Research article

Received: 22 December 2011 Revised: 17 February 2012 Accepted: 12 March 2012 Published online in Wiley Online Library: 4 July 2012

(wileyonlinelibrary.com) DOI 10.1002/jrs.4081

Pablo Picasso to Jasper Johns: a Raman study

of cobalt-based synthetic inorganic pigments†
F. Casadio,a* A. Bezúr,b I. Fiedler,a K. Muir,a T. Tradc and S. Maccagnolad
The Raman spectra of approximately 20 reference samples of cobalt-based green and violet artists’ pigments of various
provenance (present day manufactory, historical reference pigments and samples from a contemporary artist’s studio) were
acquired to assist in the identification of unknown cobalt-based pigments in works by Pablo Picasso (1881–1973) and Jasper
Johns (b. 1930). Specifically, Raman spectra were obtained for various cobalt titanate greens (Co2TiO4), highlighting variability
in peak positions because of ionic substitutions in the spinel structures of such pigments. The Raman spectra of the cobalt
violet pigments magnesium cobalt arsenate (MgxCo3-x(AsO4)2) and hydrated forms, ammonium cobalt phosphate hydrate
(NH4CoPO4*H2O), and anhydrous cobalt phosphate, Co3(PO4)2 were also recorded; some of which are presented here for
the first time. Fourier Transform Infrared spectroscopy (FTIR), x-ray fluorescence spectrometry (XRF) and x-ray diffraction
(XRD) were employed to confirm the composition of the reference materials. An optimal technique to characterize microscopic
cross sections from the studied artworks is Raman microscopy, which can also provide valuable information on the hydration
states of the examined phases. The multi-analytical methodology allowed the identification of the unknown green pigment
used by Jasper Johns as cobalt titanate green (C.I. PG 50); representing the first documented occurrence of this pigment in
the palette of a renowned contemporary artist. Both magnesium cobalt arsenate (in anhydrous and hydrated forms) and
anhydrous cobalt phosphate were identified in the Picasso painting.
This research advances the knowledge of 20th century synthetic inorganic pigments used by artists and documents their
usage in actual works of art. Copyright © 2012 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.

Keywords: cobalt titanate green; cobalt violet pigments; Raman; FTIR; XRD

Introduction mainly an unknown cobalt-based green and carbon black, with addi-
tions of viridian, ultramarine blue, and small amounts of pale cad-
For the past three decades, Raman microscopy has been an important mium yellow, iron oxide yellow, titanium white, and iron oxide
method for the characterization of pigments used in fine arts, archeol- red.[11] The complexity of the pigment mixture is not surprising, given
ogy and historic architecture.[1,2] However, although considerable effort the artist’s deep involvement in the process of creating his pieces, in-
has been devoted to the scientific analysis of historical materials and cluding mixing his own colors. Although in earlier interviews Johns
recent interest has been focused on the Raman investigation of mod- declared that he mixed wax with oil paint from tubes, in recent years
ern synthetic organic pigments,[3–5] as well as the Surface-enhanced it appears that he rather used dry >pigments mixed with wax, as con-
Raman spectroscopy study of artists’ colorants,[6] the study of synthetic firmed by the FTIR analysis of paint samples from this painting
inorganic pigments has garnered comparatively little attention.[7,8] (Fig. S1). Recent correspondence with John’s studio assistant revealed
This work was prompted by the in-depth analysis of the paintings that most of the artist’s encaustic pigments came from a specific sup-
Near the Lagoon (2002–2003) (AIC 2004.16) by American painter, plier (David Davis), and although he predominantly used cadmium
sculptor and printmaker Jasper Johns (b.1930) and The Red Armchair greens, the company also supplied a pigment named permanent
(1931) (AIC 1957.72) by Pablo Picasso (1881–1973) both in the collec- green, which was suspected to be the green used in Near the Lagoon.1
tion of the Art Institute of Chicago.[9,10] Near the Lagoon is a remark-
able piece because of its monumental size (301.9  200  10.2 cm)
and complex construction using added pieces of canvas and long * Correspondence to: Francesca Casadio, The Art Institute of Chicago, 111 S.
Michigan Ave., 60603 Chicago, IL, USA. E-mail: [email protected]
strings attached to the support to form catenaries. Its surface is cov-
ered with strokes of gray encaustic, a medium very much favored †
This article is part of the Journal of Raman Spectroscopy special issue entitled
by Johns since his famous Flag paintings of the 1950s, presumably “Raman spectroscopy in art and archaeology” edited by Juan Manuel Madariaga
for the freedom it allowed in terms of paint manipulation and variety and Danilo Bersani.
of possible visual effects. Although not evident at first glance, con-
a The Art Institute of Chicago, 111 S. Michigan Ave., 60603 Chicago, IL USA
struction and color are very important in the genesis of this work of
art. A close observation revealed that before the gray was applied, b The Museum of Fine Arts, Houston, PO Box 6826, TX 77265-6826 USA
the picture was initially painted with predominantly primary colors
– red, yellow, and blue. Also present and applied above the different c Department of Chemistry and Environmental Sciences, University of Texas at
Brownsville, 80 Fort Brown, M0-1.128, Brownsville, TX 78520 USA
shades of gray encaustic are drips of the primaries, various grays and
an intense green. Of particular interest was the green paint, which
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d Università di Bologna, Microchemistry and Microscopy Art Diagnostic Laboratory

was found to contain beeswax and a complex mixture of pigments, (M2ADL), via Guaccimanni 42, 48100 Ravenna Italy

J. Raman Spectrosc. 2012, 43, 1761–1771 Copyright © 2012 John Wiley & Sons, Ltd.
 F. Casadio et al.

Pablo Picasso’s painting The Red Armchair (1931) (oil and Ripolin Table 1. List of cobalt-based green pigments analyzed in this study
on panel; 131.1  98.7 cm) depicts the blond female figure of
Pigment sample Description
Marie-Thérèse Walter, the artist’s companion and muse at the time,
wearing a fur stole and sitting in a red and maroon-striped arm- 2004.146; sample #4 Micro-sample from a green drip in
chair. The painting is executed on wood panel and is characterized Jasper Johns’ Near the Lagoon.
by bright colors and a thick glossy paint surface, elements that Cobalt green 44100 Cobalt green, C.I. pigment green 50,
would become the hallmark of the Marie-Thérèse series. The back- Kremer Pigmente.
ground contains four purple areas in addition to a yellow and mus- Sherwood green 5 Cobalt titanate green spinel, C.I. pigment
tard section. The softened impasto appearance of certain passages, green 50, Shepherd Color Co.
including areas of the purple background led to the investigation Shamrock green 223 Cobalt titanate green spinel, C.I. pigment
of the hypothesis that Picasso mixed artists’ tube oil colors with a green 50, Shepherd Color Co.
fluid, non-artists’ white paint, such as Ripolin – a popular brand Fairway green 260 Cobalt titanate green spinel, C.I. pigment
of French house paint.[12] Although the specific use of Ripolin green 50, Shepherd Color Co.
paints in the Red Armchair is discussed in detail elsewhere,[13] this Kelly green V-11633 Cobalt titanate green spinel, C.I. pigment
work deals with the issue of precisely identifying the colorants in green 50, Ferro Corporation.
the purple areas of the painting, in order to evaluate whether they Permanent green dark David Davis pigments, sample from
are characteristic of tube paints or non-artists’ paints. Jasper Johns’ studio
The detection of cobalt greens and violets in these two paintings, Permanent green medium David Davis pigments, sample from
respectively, provided the motivation for a systematic study of these Jasper Johns’ studio
pigments to establish a reference set of Raman spectra, because Permanent green light David Davis pigments, sample from
published Raman spectra were not available for comparison. Jasper Johns’ studio
Bouchard and Gambardella recently provided detailed vibrational
characterization of synthetic cobalt blue pigments;[14] however, to
the best of the authors’ knowledge, only the Raman spectra for
erythrite (the octahydrate of cobalt(II) arsenate) and its partially same time as other titanate and chromite pigments (chromium
dehydrated forms have been published in the literature,[15,16] but or nickel antimony titanate yellows, brown and black titanates
these constitute only a minor component of commercial cobalt and cobalt chromite greens) and were intended as an improve-
violet pigments.[17] Cobalt titanate greens, on the other hand, con- ment for colored pigments that were physically blended with ti-
sist of solid solutions rather than stoichiometrically restricted mixed tanium dioxide. When used for exterior purposes, blends had a
salts, and the variation in manufacturing processes and composition tendency to chalk unevenly. The titanates chalked less, and if
is reflected in a slight variability in their spectra. Thus, although the they did chalk, they tended to chalk more uniformly.[19] Cobalt
spectrum of Kremer’s cobalt green (PG 19, K44100) has been previ- titanate greens are prepared from mixtures of the different cobalt
ously presented in an online database of artists pigments,[18] it was and titanium oxides by a calcination process at very high tem-
considered advantageous to substantially extend the available peratures (ranging from 800 to 1100  C, depending on the spe-
reference spectra of cobalt titanate pigments, so as to encompass a cific pigment).[19] The crude pigment is then ground to a very
wide range of possible band shifts because of the introduction and fine powder. Nowadays, the pigment is finished by micronizing
varying proportions of different metal ions in specific formulations. and washing and drying. According to a 1934 patent, the shade
Approximately 20 reference samples of artists’ cobalt-based of the green pigment could be altered by either calcining at a
green and violet pigments from various manufacturers, including higher temperature or by increasing the time at a lower temper-
some historical samples from Lefranc et Cie. and contemporary ature.[20] The color or property of the pigment can also be mod-
samples provided directly by Jasper Johns’ studio were fully char- ified by introducing different metal ions into the formulation.[19]
acterized (Tables 1 and 2). Complementary techniques such as The pigment’s composition may in fact include any one or a com-
Fourier Transform Infrared spectroscopy (FTIR), x-ray fluorescence bination of the modifiers CaO, Li2O, MgO, Fe2O3 NiO, Sb2O5 or
spectrometry (XRF) and x-ray diffraction (XRD) were used to con- ZnO. Chemically the metal oxides ionically diffuse into each other
firm the composition and check the purity of the reference mate- during the calcination process forming an inverse spinel structure
rials (Tables 2 and 3 and Figs S6–S27). Given the severe volume that endows these pigments with superior stability. Other struc-
restrictions of samples from high-value works of art, the only tures may also be possible. The titanates and chromites are in fact
techniques that were actually applicable to the characterization considered high performance pigments because of their durabil-
of microscopic cross sections from the studied artworks were ity, lightfastness, and weatherability properties.[21]
scanning electron microscopy with energy dispersive x-ray spec- Early uses were in the ceramics industry and in the 1970s for the
trometry and Raman microscopy, the latter providing also impor- solid plastics market, for use in making vinyl siding.[19] Other more
tant molecular and hydration information on the pigments under recent uses are in plastics for food containers, durable coatings,
investigation. Other alternative techniques of unambiguous iden- toners for photocopiers, and artist’s paints. Cobalt titanate first
tification may also include x-ray microdiffractometry as well as appears in the Color Index in 1982 designated as C. I. 77377, CI Pig-
polarized light microscopy of loose samples. ment Green 50 with the chemical formula given as Co2TiO4.[22,23]
As highlighted previously, it should be borne in mind that the term
‘cobalt titanate greens’ may indicate compositions comprising
Cobalt titanate green pigments: history, various metals and possibly more than one crystal structure. Cobalt
manufacture and use titanate nanoparticles are also of great interest beyond their use
as pigments because of their potential applications in catalysis,
Cobalt titanate greens (Co2TiO4) are mixed metal oxides that photocatalysis, electronics, and photonics, effectively extending
1762

were discovered in the 1930s. They were developed around the the absorption range of titania into the visible domain.[24,25]

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Picasso to Johns: a Raman study of cobalt-based synthetic inorganic pigments

Table 2. List of cobalt violet pigments (dry pigments and paints) analyzed in this study
Pigment sample Description Compositiona, b
CI name

Cobalt violet dark Kremer, #277, AIC collection, Co3(PO4)2 (Raman, XRD) and Co3(PO4)2*8H2O (FTIR) C.I. 77360 PV 14
dry pigment
Violet de cobalt Lefranc, Forbes collection (AIC V10) Co3(PO4)2 (Raman, FTIR, XRD) C.I. 77360 PV 14
dry pigment
Cobalt violet Fezandie and Sperrle, AIC collection, Co3(PO4)2 (Raman) and Co3(PO4)2*8H2O (FTIR) C.I. 77360 PV 14
dry pigment
Violet de cobalt Lefranc AIC collection #2007.1 Co3(PO4)2 (Raman,XRD, FTIR) Co3(PO4)2*8H2O (XRD) C.I. 77360 PV 14
historical oil tube paint- out
Violet de cobalt Lefranc historical oil tube from Co3(PO4)2 (Raman, XRD, FTIR); Mg3-xCox(AsO4)2 (Raman) C.I. 77360 PV 14
1930–1935 painted on canvas
(C2RMF, Paris)
Cobalt violet light Kremer, AIC collection, dry pigment NH4CoPO4*H2O (Raman, FTIR, XRD); XRD also identifies C.I. 77362 PV 49
cobalt ammine phosphate hydrate [Co3(NH3)4.8(PO4)2*9H2O],
cobalt nitrate hydroxide [Co5(O9.48H8.52)NO3], and cobalt
phosphate hydrate [Co3(PO4)2*8H2O] as minor phases
Violet 102 Shepherd Color Company, AIC NH4CoPO4*H2O (Raman, FTIR, XRD); XRD also identifies cobalt C.I. 77362 PV 49
collection, dry pigment ammine phosphate hydrate [Co3(NH3)4.8(PO4)2*9H2O], cobalt
nitrate hydroxide [Co5(O9.48H8.52)NO3], and cobalt phosphate
hydrate [Co3(PO4)2*8H2O] as minor phases
Pure cobalt phosphate Permanent pigment, AIC collection, NH4CoPO4*H2O (Raman) C.I. 77362 PV 49
dry pigment
Cobalt violet light Weber, Forbes collection (AIC V13), Mg3-xCox(AsO4)2 (FTIR, Raman) and hydrated forms (Raman)
dry pigment
Cobalt violet Weber, Forbes collection (AIC V14), Mg3-xCox(AsO4)2 and hydrated forms (FTIR, Raman)
dry pigment
Violet de cobalt 1927 Lefranc, Forbes collection (AIC V8), Mg3-xCox(AsO4)2 (FTIR, Raman)
dry pigment
Cobalt violet Rowney, Forbes collection (AIC V12), Mg3-xCox(AsO4)2 (Raman)
dry pigment
1957.72 sample #1 Light purple paint from Picasso’s Co3(PO4)2 (Raman, SEM/EDS), Mg3-xCox(AsO4)2, C.I. 77360 PV 14
Red Armchair, 1931 (Raman, SEM/EDS) and hydrated forms (Raman)

XRD, x-ray diffraction; FTIR, Fourier Transform Infrared spectroscopy; SEM/EDS, Scanning electron microscopy with energy dispersive x-ray analysis.
a
The analytical technique that unambiguously identified the individual phases listed is specified in parenthesis.
b
Components listed in italics are present as minor/trace phases.

Cobalt violet pigments: history, manufacture information; however, Corbeil et al. found that all historic
arsenate-containing pigment reference materials and samples
and use from artwork contained primarily magnesium cobalt arsenate
The term ‘cobalt violet’ pigment does not refer to a specific (Mg2Co(AsO4)2), which is likely the compound that 19th
cobalt-containing compound, but rather a group of compounds century sources described as ‘a compound or a mixture of
exhibiting a range of hues from light pinkish-purple to deep cobalt oxide and magnesium oxide’.[17] Cobalt violet pigments
purple-violet (Fig. S2). For a detailed discussion of the history have been identified in paintings starting from the mid-19th
and properties of five key pigment compounds – magnesium century.[17,23] Syntheses of the hydrated versions of cobalt
cobalt arsenate, cobalt phosphate, cobalt phosphate hydrate, phosphate, the tetrahydrate and octahydrate, date to 1933;
ammonium cobalt phosphate hydrate, and lithium cobalt however, only the octahydrate is considered to have a violet
phosphate – the reader is referred to Corbeil et al.[17] Cobalt hue and has been identified as the major component of
ammonium arsenate is also sometimes mentioned in the pig- a dry pigment, ‘Standard Lack Kobaltviolett’.[17] Another
ment literature.[23] Cobalt phosphate (Co(PO4)2) and cobalt hydrated cobalt violet, ammonium cobalt phosphate hydrate
arsenate (Co3(AsO4)2) were first synthesized in the 19th cen- (NH4CoPO4*H2O), has only been identified in paintings from
tury, and distributors of artist’s materials referred to them as the mid-20th century and later despite its description in chem-
dark and light cobalt violet, respectively.[17] An artist like Pablo istry references from 1864. Lithium cobalt phosphate (LiCoPO4)
Picasso would have most likely encountered cobalt violet oil is a relatively new pigment – first discussed in 1941 – which, so
paints through Lefranc et Cie. The company marketed the dark far, has not been identified on artworks. These two latter
version as ‘violet de cobalt foncé (phosphate de cobalt)’ and pigments are the only cobalt violet pigments that remain
the light version as ‘violet de cobalt clair (arséniate de cobalt)’. available to artists today, as arsenic-based compounds were
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Winsor & Newton’s 1928 catalog provided the same chemical discontinued starting in the 1960s.[23]

J. Raman Spectrosc. 2012, 43, 1761–1771 Copyright © 2012 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/jrs
 F. Casadio et al.

Table 3. X-ray fluorescence spectrometry (XRF) and x-ray diffraction (XRD) analysis of cobalt titanate greens
Pigment Elemental composition detected by XRFa Phases detected by XRDb

2004.146; sample #4 Ni, Ti, Co, Zn, Fe, (Cr, Ca)c N/A
Cobalt green 44100 Ni, Ti, Co, Zn, Cr, Ba, S, Si NiZnTiO4 nickel zinc titanium oxide (35–1372); Co2TiO4 cobalt titanium
oxide (39–1410); BaSo4 (24–1035)
Shamrock green 223 Ni, Co, Zn, Ti, (Si, Ca, S) NiZnTiO4 nickel zinc titanium oxide (35–1372); Co2TiO4 cobalt titanium
oxide (39–1410); NiTiO3 nickel titanium oxide (33–0960)
Sherwood green 5 Ni, Zn, Ti, Co, Sb, (Si, S) NiZnTiO4 nickel zinc titanium oxide (35–1372); Co2TiO4 cobalt titanium
oxide (39–1410); NiTiO3 nickel titanium oxide (33–0960)
Kelly green V-11633 Ni, Ti, Co, Zn, (Fe, Ca, Si, Al) NiZnTiO4 nickel zinc titanium oxide (35–1372); Co2TiO4 cobalt titanium
oxide (39–1410); NiTiO3 nickel titanium oxide (33–0960)
Fairway green 260 Ni, Ti, Co, Zn, (Ca, Si, S) NiZnTiO4 nickel zinc titanium oxide (35–1372); Co2TiO4 cobalt titanium
oxide (39–1410); NiTiO3 nickel titanium oxide (33–0960)
Permanent green dark Ni, Zn, Co, Ti, Cr, Cd, Sb, Pb, (Ca, Fe) (Co0.255Fe0.745)(Co0.745Fe1.255)O4 cobalt iron oxide (01-074-3419)d; titanium
Permanent green medium Ni, Zn, Co, Ti, (Fe) oxide (rutile) TiO2 (PDF 03-065-0190); aluminum oxide trihydrate (nordstrandite)
Permanent green light Ni, Ti, Zn, Co, Sb Al2O3*3H2O (00-015-0141); nickel oxide (bunsenite) NiO (PDF 01-071-1179)
a
Underlining represents elements detected in major amounts, regular font represents medium level, and brackets represent minor or trace elements
based on a qualitative assessment of relative peak heights, and considering that all these pigments are contained in a similar matrix.
b
Italicized phases are present at minor/trace levels. The nickel zinc titanium oxide (NiZnTiO4) and cobalt titanium oxide (Co2TiO4) phases have cubic
crystal structures.
c
The elements detected in this case actually reflect the composition of the entire green paint drip and underlying layers and are not related to the
pigment only, contrary to the pure pigment powders described below.
d
Although the lattice parameters and crystal structures are similar to cobalt ferrite spinel, because XRF analysis detects only trace level Fe, cobalt
ferrite cannot be the main phase here, but it is actually a highly substituted one that is present (with Ni, Ti, Zn).

Experimental details the surface of KBr pellets of violet pigments and on cross sections
from the works of art using a Horiba Jobin-Yvon Labram 300
Pigment samples confocal Raman microscope, equipped with Andor multichannel
Five different varieties of PG50 were obtained from the manufac- air cooled open electrode charge-coupled device detector
turers Ferro Corporation, Shepherd Color Co. and Kremer
Pigmente; details of the pigments are provided in Table 1 and
Fig. S3. Additionally, three samples of David Davis permanent
green in light, medium, and dark shades were generously sup-
plied by Jasper Johns’ studio (Table 1). The cobalt violet pigment
samples included powdered pigments from a historical reference
collection (the Forbes pigment study collection2),[26] samples of
early 20th century Lefranc oil paint tubes of cobalt violet, and
modern cobalt violets, encompassing the following compounds:
magnesium cobalt arsenate (Mg3-xCox(AsO4)2 and hydrated
forms), ammonium cobalt phosphate hydrate (NH4CoPO4*H2O),
cobalt phosphate octahydrate (Co3(PO4)2*8H2O), and anhydrous
cobalt phosphate, Co3(PO4)2 (Table 2 and Figs S2 and S4). Reference
pigments received from the various manufacturers were first
checked for pigment purity with XRD and subsequently also
analyzed with FTIR spectroscopy and XRF prior to Raman analysis
as detailed in Tables 2 and 3.
A sample of green paint was collected from Johns’ Near the
Lagoon from a thin dark green drip in the bottom right quadrant
of the painting (Fig. 1). A microscopic sample of light purple paint
from Picasso’s The Red Armchair was excised with a scalpel blade
from the light purple stripe in the background of the painting, in
the upper right quadrant (Fig. S5).

Figure 1. Jasper Johns, Near the Lagoon (2002–2003); encaustic on can-

Instrumental methods of analysis vas, 301.9  200  10.2 cm; through prior gift of Muriel Kallis Newman in
memory of Albert Hardy (AIC 2004.16). A sample of the green drip illus-
Raman microspectroscopy – Raman spectra were collected from
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trated in this detail of an area located in the bottom right quadrant of

particles in loose powders of the green reference pigments, at the painting was removed for analysis.

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Picasso to Johns: a Raman study of cobalt-based synthetic inorganic pigments

(1024  256) and a dispersive grating with 1800 grooves/mm. Results and discussion
A He-Ne laser (l0 = 632.8 nm) and a frequency doubled Nd:Yag
solid state laser (l0 = 532 nm) were used for excitation of the Cobalt-based green pigments
violet and green pigments, respectively, focused through a Microscopical examination of the pigment particles supplemen-
100 objective on to the samples. As the main Raman scatter- ted by XRD, XRF, FTIR and Raman spectroscopy highlighted the
ing peak of the cobalt titanate greens appears to shift amongst presence of a number of additives in the commercial formula-
the different pigment varieties depending on type and amount tions of cobalt titanate green. In particular, the green powders
of transition metals substitution, to guarantee the highest also contain yellow and blue particles to reinforce and adjust
accuracy and inter-comparison of the measurements a silicon the color. The pigments from Jasper Johns’ studio, for example,
reference was run to check calibration before and after each show a variety of other Ti-based and Co-based compounds
measurement, and all measurements were carried out during (Fig. 2), such as nickel titanate yellow ((Ti, Ni, Sb)O2, with Raman
the course of the same hour to guarantee the smallest possible bands at 127 m(br), 240 m(br), 440 s, 615 s, 681w(br) cm 1),[27]
instrumental band drift. Samples from the artworks were inves- and cobalt blue (CoxAl3-xO4, with Raman bands at 203 vs; 516
tigated with a solid state diode laser excitation (l0 = 785.7 nm) vs cm 1).[14] Although the spectrum of nickel titanate yellow
to minimize interference because of fluorescence of the binding has been published in the literature, this is the first documented
media. Laser power at the samples was kept very low (never occurrence of the pigment in the actual palette of a contempo-
exceeding 1 mW) by a series of neutral density filters in order rary artist.[27] Kremer’s Cobalt green 44100 is extended with
to avoid any thermal damage. barium sulfate (Fig. 3(c)), whereas the David Davis greens contain
Fourier-Transform Infrared microspectroscopy – a Bruker Tensor small quantities of TiO2 in its rutile form.
27 FTIR spectrophotometer with deuterated triglycine sulfate The FTIR spectrum of the green sample from Jasper John’s
detector, coupled to Hyperion 2000 automated FTIR microscope Near the Lagoon shows a good correlation with the FTIR spectra
with nitrogen cooled mid-band mercury cadmium telluride of the reference materials, as well as with a published spectrum
detector was used. The spectra were collected between 4000 of Kelly Green (C.I. PG 50),[28] based on two broad bands cen-
and 400 cm 1 at a resolution of 4 cm 1. They are illustrated in tered at approximately 600 and 440 cm 1 (Figs S1, S6–S8); how-
Figs S6–S8 and S18–24. ever, many metal oxide vibrations occur in the low wavenumber
X-ray fluorescence spectrometry – x-ray fluorescence spectra region of the infrared spectrum. Furthermore, the infrared spectra
of the reference pigment powders were collected using a of mixed phase titanate pigments are not very different from that
Bruker ArTAX air-path micro-focus x-ray spectrometer, equipped of their parent titanium dioxide, and differentiation between vari-
with 1 mm diameter collimator, excitation tube with Mo target ous titanates is often difficult with FTIR spectroscopy alone.[29,30]
(max 50 kV, max 1 mA), and X-Flash x-rayW detector (energy Raman spectroscopy, on the other hand, allows the unambiguous
resolution 160–165 eV for Mn-Ka). A portable Bruker Tracer III-V identification of Jasper Johns’ green pigment as cobalt titanate
energy dispersive x-ray fluorescence spectrometer was also green. The Raman spectra of the five commercial reference pig-
used for in-situ analysis of the Johns and Picasso paintings. The ments are illustrated in Fig. 3 and their bands detailed in Table 4.
XRF spectrometer is equipped with an Rh transmission target, The strong feature centered approximately at 700 cm 1 has been
and Ag-free SiPIN detector (5 mm diameter aperture, resolution observed also in other titanates and spinels and assigned to the
~ 175 eV for Mn-Ka).
Powder x-ray diffraction – the green reference pigments were
analyzed at Northwestern University (Evanston, IL) with a Scintag
model XDS2000 diffractometer, equipped with Cu radiation
l = 1.55418 Å running at 40 kV and 20 mA. The system also uses
a GeLi solid state EDX detector. The violet pigments and David
Davis permanent green pigments were analyzed at the University
of Texas at Brownsville. Phase identification was performed using
a Bruker D2Phaser powder X-ray diffractometer. 2θ values were
collected from 20 to 90 using Co Ka radiation (l = 1.79026 Å)
with a current flux of 10 mA and an acceleration voltage of
30 kV, a step size of 0.005 and a counting time of 6 s per step.
Consequently, the analysis time for each sample was 23 h and
20 min. An iron filter for Co-Kb radiation was employed (Fe-foil,
thickness 0.01 mm, to suppress Co-Kb radiation down to about
1% of Co-Ka level). All samples were rotated at 12 rpm during
analysis. A zero background specimen holder made from Si
(911) single crystal material was used for all samples except for
‘Violet de Cobalt – Lefranc (AIC 2007.1)’. Si(911) surface avoids
the excitement of Bragg reflections in the whole 2θ range.
Because of the nature of the ‘Violet de Cobalt –Lefranc (AIC
2007.1)’ sample – which is a paint film as opposed to a pigment
powder – an adjustable-elevation specimen holder was used
instead. All the XRD scans were collected at ambient tempera- Figure 2. Raman spectra (l0 = 532 nm) of (a) yellow particles in David
Davis permanent green dark (20 s, two times; pigment identified as
ture, and the phases were identified using the International nickel titanate yellow); (b) blue particle in David Davis permanent green
Center for Diffraction Data database. All the XRD spectra are
1765

light (80 s, three times; pigment identified as cobalt blue with cobalt
illustrated in Figs S9–15 and S25–28. titanate green).

J. Raman Spectrosc. 2012, 43, 1761–1771 Copyright © 2012 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/jrs
 F. Casadio et al.

0 to 0.65, with substitution of Fe3+ ions in cobalt ion sites.[35] Bands

below 300 cm 1 have been ascribed to lattice vibrations and to the
vibrational modes of tetrahedral cations.[34,35]
Interestingly, the cobalt titanate greens from Jasper Johns’ stu-
dio appear to exhibit a different crystal structure, with different
lattice parameters than the five commercial cobalt titanates
greens, as evidenced from their XRD patterns (Figs S9–S15). The
reflections in the diffractograms of the David Davis greens dem-
onstrate the similarities amongst these pigment powders and
match very well with reference patterns for cobalt ferrites (CoO.
Fe2O3); however, the XRF spectra of these pigments only show
Fe at trace levels (Table 3), whereas showing high tenors in Ti,
Zn and Ni (Figs S16a,b and S17). Therefore, one can speculate
that in the cobalt ferrite spinel structure of these pigments Fe3+
ions have likely been replaced by titanium or nickel, whereas
the Fe2+ sites may have been replaced by zinc or nickel. Thus,
although the spinel structure is preserved, the color of the pig-
ments is green (not black or dark gray like many magnetic cobalt
ferrite pigments), and peaks are displaced at higher 2θ values
than for the other commercial cobalt titanate pigments, whose
Figure 3. Raman spectra of five commercial reference cobalt titanate main phases are consistently identified as Co2TiO4 and NiZnTiO4
green pigments (l0 = 532 nm) (a) Fairway green 260 (15 s, four times); (Figs S9–S12). Interestingly, the different lattice parameters and
(b) Shamrock green 223 (12 s, ten times); (c) Kremer cobalt green
44100 (20 s, four times; the asterisk marks the peak related to barium degrees of ionic substitution in the green cobalt-spinels present
sulfate); (d) Sherwood green 5 (20 s, four times); (e) Kelly green V-11633 in the David Davis pigments appear to cause a more or less pro-
(20 s, four times). nounced shift in the A1g mode vibration to higher wavenumbers,
as illustrated in Table 4.
Ultimately, by comparison with the reference spectra collected,
highest wavenumber vibrational mode (symmetric stretching the spectrum observed for the Jasper Johns sample, showing
mode A1g) of CoO6 octahedra, or MnO6 octahedra in CoTiO3 nano- Raman bands centered at 163vw, 224w, 267vw, 279sh, 325w,
particles and MnTiO3 nanoparticles, respectively,[31–33] so it can 380w, 522sh, and 699vs cm 1, can be convincingly matched with
similarly be attributed to the symmetric stretching mode of CoO6 the pigment Kelly Green or with David Davis Green pigment in
in the Co2TiO4 green pigments. Band broadening and peak shifts medium shade (Fig. 4). Unfortunately, given the scarcity of mate-
– particularly noticeable for the main band – can be linked to rial available from the painting and unavailability of a system for
cation disorder because of the introduction of different metal ions micro-diffraction, it was not possible to perform XRD analysis and
in the spinel lattice (such as for example Ni, Zn, Fe, Cr, and Sb, thus clarify which one of the two spinel structures the actual pig-
detected in the reference pigments with XRF), to affect the final ment used by Jasper Johns belongs to.
hue of the various formulations or modify the pigment properties.
These ions distort the lattice of the spinel structure, affecting the
Cobalt violet pigments
octahedrally coordinated cobalt and tetrahedrically coordinated
titanium in different ways, and this phenomenon is reflected in The 12 cobalt violet reference pigments analyzed can be clearly
each Raman spectrum.[34,35] For instance, it has been observed divided into three main groups based on their unique Raman
that for cobalt based magnetic spinels such as Co3-xFexO4, the features: cobalt phosphates, magnesium-cobalt arsenates and
A1g peak, centered at 689 cm 1 for pure cobalt oxide can be dis- ammonium-cobalt phosphates (Tables 2 and 5). Specifically, the
placed to lower wavenumbers up to 34 cm 1 when x varies from pigment powders of samples Kremer cobalt violet dark; Lefranc

Table 4. Observed Raman bands for the reference cobalt titanate green samples and the sample from the painting by Jasper Johns (l0 = 532 nm)
2004.146; Sherwood Fairway green Shamrock Kelly green Cobalt green Permanent green Permanent green Permanent green
sample #4 green 5 260 green 223 V-11633 44100 dark medium light

163 vw 159 w 170 m 174 w 167 vw 170 m 172 w 173 w, br 172 w

224 w 218 w 220 vw
227 w 230 w 236 w 224 m 230 w 237 w 229 w
267 vw 268 vw 276 sh
279 sh 282 sh 280 vw 298 sh 282 sh 273 vw
325 w 328 m 332 m 335 m 326 m 332 m 337 m 331 w 344 w
380 w 378 w 384 w 387 w 380 w 384 w 387 w 383 w 380 vw
474 sh 476 sh 476 sh 458 sh 476 sh 487 sh
522 sh 516 m, br 523 m, br 522 m, br 523 m, br 517 m, br 522 m, br 522 m, br 530 m, br
699 vs 700 vs 707 vs 704 vs 698 vs 703 vs 706-718 vs 701vs 721 vs
1766

1
All spectra were recorded within the same hour, after calibration with the 520.7 cm line of silicon.

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Picasso to Johns: a Raman study of cobalt-based synthetic inorganic pigments

between 1 and 3 mm) thus one may have to probe several

tens of particles before finding one that is hydrated, which
is very time-consuming, whereas with FTIR and XRD, one is
more readily able to probe ‘bulk’ properties of the materials
under study.
Cobalt ammonium phosphate hydrate (NH4CoPO4*H2O) was
identified as the coloring agent in the reference pigments Kremer
Cobalt violet light; Violet 102, Shepherd Chemical Company and
Pure Cobalt phosphate, Permanent pigment, with Raman bands
centered at 185w, 222vw, 260w, 363vw, 432vw, 483vw, 546w,
622vw, 939vs, 1063w, 1112vw, 1448vw, 2782vw, 3068vw(br),
3374vw(br) cm 1. The spectra collected on the various pigments
are rather consistent, and only the triplet at 185, 222, 260 cm 1
seems to have variable relative intensity (Fig. 6). In addition to
ammonium cobalt phosphate hydrate, which is the major
phase, XRD reveals additional reflections attributed to cobalt
ammine phosphate hydrate (Co3(NH3)4.8(PO4)2*9H2O), cobalt
Figure 4. Raman spectra (l0 = 532 nm) of (a) a sample of green paint nitrate hydroxide (Co5(O9.48H8.52)NO3), and cobalt phosphate
from Jasper Johns, Near the Lagoon, 2002–2003 (AIC 2004.16) (15 s, ten
hydrate (Co3(PO4)2*8H2O), present at minor to trace levels
times); (b) the reference commercial cobalt titanate pigment Kelly green
V-11633 (20 s, four times); (c) David Davis permanent green medium pig- (Table 2, Figs S26 and S27).
ment, from Jasper Johns’ studio (12 s, three times). Lastly, magnesium cobalt arsenate (Mg3-xCox(AsO4)2) was
identified in the reference pigment powders Weber cobalt
violet light (Forbes collection, AIC V13); Lefranc violet de cobalt
violet de cobalt (Forbes collection, AIC V10); cobalt violet, (Forbes collection, AIC V8) and Rowney cobalt violet (Forbes
Fezandie and Sperrle; Lefranc violet de cobalt (historical oil tube collection, AIC V12), as well as in the paint tube Lefranc violet
paint-out, AIC 2007.1) and Lefranc violet de cobalt (historical oil de cobalt (C2RMF, which also contains cobalt phosphate, as
tube, C2RMF, also containing magnesium cobalt arsenate) all mentioned previously). The analysis of the Weber cobalt violet
contain Co3(PO4)2. Of the group of the vivianite minerals (with pigment (Forbes V14) also shows the presence of hydrated
general formula AII3(XVO4)2*8H2O where A=Fe, Mg, Ni, Co or Zn forms with a strong sharp Raman peak at 3059 cm 1 (Fig. 6)
and X=P or As) only the Raman spectra of erythrite (A=Co, and several bands in the FTIR spectrum (Fig. S24), which are
X=As),[16,17] vivianite (A=Fe; X=P),[36,37] and annabergite (A=Ni, not present in the Lefranc violet de cobalt (Forbes collection,
X=As)[37] have been fully described. Although the Raman spec- AIC V8), Weber cobalt violet light (Forbes V13) and Rowney
trum of cobalt phosphate has not been published in the litera- cobalt violet (Forbes collection, AIC V12) (Figs S22 and S23).
ture, the available data on vivianite minerals by Piriou and Raman bands at 202vw, 368w(br), 418w(br), 507w, 737w (br),
Poullen[36] allow one to make inferences on the particular modes 765w(sh), 834m(sh) and 867vs cm 1 are observed (Fig. 6).
deriving from vibrations of PO4 groups amongst those acquired Typically, bands between 500 and 300 cm 1 have been attrib-
from the violet pigments examined (Fig. 5): 147 s, 193vs, 216vw, uted to out of plane bends of the AsO4 unit, between 300
234w, 263vw 290w, 335m, 451w (n2PO4), 478w, 559w (n4PO4), and 200 cm 1 to in-plane bends; and below 200 cm 1 to lattice
609w, 624w (n4PO4), 969 s (n1PO4), 1013m (n3PO4), 1034m, vibrations. The peaks between 870 and 750 cm 1 are, on the
1059vw, 1082vw, 1115vw cm 1. Because reference spectra were other hand, attributed to anti-symmetric and symmetric stretch-
recorded on KBr pellets of the pigments that were prepared for ing modes of AsO4.[16]
FTIR spectroscopy (Figs S18 and S21), allowing analysis of single To summarize, this study of a wide variety of reference pig-
grains of pigment that are locked into fixed position in the KBr ments shows that, similarly to FTIR spectroscopy (Figs S18–S24),
matrix, the Raman spectra show strong crystal orientation effects, Raman spectroscopy proves a very valuable tool to quickly and
giving high variability in the relative intensities of the bands efficiently discriminate amongst different types of cobalt violet
between 100 and 700 wavenumbers (Fig. 5). The presence of pigments and is in most cases very efficient at clarifying
the octahydrate form (Co3(PO4)2*8H2O) was also detected in whether the compounds are present as anhydrous or hy-
the pigments Kremer cobalt violet dark; cobalt violet, Fezandie drated crystals. Because of the enhanced sensitivity and spa-
and Sperrle, and Lefranc violet de cobalt (AIC 2007.1). In most tial resolution of Raman spectroscopy, it was possible to
cases, only FTIR was able to identify the hydrate phases, and analyze single pigment grains and thus, after probing several
in one case XRD only (Lefranc violet de cobalt (AIC 2007.1, dozen particles, successfully identify hydrated phases also in
Fig. S28)), which seems to suggest that phases with coordi- materials that, when analysed with XRD or FTIR by other
nated water are not the predominant forms, and in fact, they authors did not appear to contain hydrated compounds.[17]
were neither detected nor described by Corbeil et al. for Because of its superior lateral resolution, Raman spectroscopy
Kremer cobalt violet dark (Fig. S25).[17] That is, when the hy- was the only viable technique amongst the ones available for
drated phases are not the main components of the pigment this study to identify the pigments of the Picasso painting un-
powder or painted layer, Raman microspectroscopy may not der investigation. Specifically, a cross section was made of a
be the most efficient technique at detecting such hydrated sample taken from an area of light purple paint in Pablo
phases. In fact, FTIR microspectroscopy probes areas that mea- Picasso’s The Red Armchair, 1931, (AIC 1957.72), which allowed
sure on average 6–50 mm, while Raman micro-spectroscopy has the visualization of the presence of two different purple pig-
a high spatial resolution (depending on the laser line and nu- ments. Scanning electron microscopy with energy dispersive
1767

merical aperture of the objectives used, this can roughly range x-ray analysis (SEM/EDS) elemental maps of the cross section

J. Raman Spectrosc. 2012, 43, 1761–1771 Copyright © 2012 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/jrs
 F. Casadio et al.

Table 5. Observed Raman and Fourier Transform Infrared spectroscopy (FTIR) bands for one representative example of each type of cobalt-violet
reference pigments amongst those listed in Table 2 (l0 = 633 nm) and the sample from the painting by Pablo Picasso (l0 = 785 nm)

Pigment namea Components FTIR peaks (cm 1) Raman peaks (cm 1)

Cobalt violet light, Kremer (AIC) NH4CoPO4*H2O 562 185w

[Violet 102 Shepherd Color Company; pure cobalt 625 222vw
phosphate Permanent pigment] 782 260w
937 363vw
974 432vw
1044 483vw
1102 546w
1431 622vw
1468 939vs
1668 1063w
1867 1112vw
2784 1448vw
2940 2782vw
3049 3068vw, br
3212 3374vw, br
3405

Lefranc violet de cobalt (AIC Forbes V10) Co3(PO4)2 452 147 s

[Kremer Co violet dark; Lefranc violet de cobalt (Forbes V10); 510 193vs
cobalt violet Fezandie and Sperrle; Lefranc violet de Cobalt 560 216vw
(paint-out 2007.1, AIC); Lefranc violet de cobalt (C2RMF)] 605 234w
956 263vw
1008 290w
1045 335m
1632 451w
2930 478w
3450 559w
609w
624w
969 s
1013m
1034m
1059vw
1082vw
1115vw
Lefranc violet de cobalt 1927 (Forbes V8) Mg3-xCox(AsO4)2 449 204vw
and Mg3(AsO4)2
[Lefranc violet de cobalt (C2RMF); Rowney cobalt violet 487 351w, br
(Forbes V12)] 603 375w, sh
860 423w, br
1645 509w
3452 738vw, br
765vw, sh
837m, sh
867vs

Weber cobalt violet (Forbes V14) Mg3-xCox(AsO4)2 and 451 199vw

Mg2Co(AsO4)2*nH2O
[Weber cobalt violet light (Forbes V13)] 492 376vw
737 423w
858 505vw
1587 737vw
1637 834m
1676 867vs
3059 3059vs
3173
1768

3455

(Continues)

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Picasso to Johns: a Raman study of cobalt-based synthetic inorganic pigments

Table 5. (Continued)

Pigment namea Components FTIR peaks (cm 1) Raman peaks (cm 1)

Pablo Picasso, The Red Armchair (1957.72); sample #1 Co3(PO4)2 Below detection limit 148 s
dark purple particles 194vs
215vw
230w
265vw
289w
338m
491m
560m
608w
621w
968 s
1012m
1036m
1064vw
1082w

Pablo Picasso, The Red Armchair (1957.72); sample #1 light Mg3-xCox(AsO4)2 860b 204vw
purple particles 351w, br
375w, sh
420w, br
508w
738vw, br
765vw, sh
837m, sh
865vs
a
Other reference pigments that showed very similar spectra to the one whose peaks are reported here are listed in square brackets.
b
When dispersed in a medium, many of the characteristic pigment bands are obscured in the FTIR spectrum, and only the most intense peak of the
magnesium cobalt arsenate is visible.

Figure 5. Raman spectra (l0 = 633 nm) recorded on KBr pellets of the
deep violet, cobalt-phosphate based (Co3(PO4)2) reference pigments: (a)
and (b) Kremer cobalt violet dark, showing variability in band intensity Figure 6. Raman spectrum (l0 = 633 nm) of the violet reference pigment:
because of orientation of the pigment particles (90 s, two times); (c) (a) Kremer cobalt violet light (60 s, three times, after multipoint baseline
Lefranc violet de cobalt (Forbes collection, AIC V10) (55 s, five times, after correction, pigment identified as NH4CoPO4*H2O); (b) Weber cobalt violet
multipoint baseline correction). (Forbes V14) (10 s, 2 times, after multipoint baseline correction, pigment
identified as hydrated Mg3-xCox(AsO4)2).

revealed that the pigment particles with a reddish-purple Subsequently, Raman microscopy allowed the targeting of
color contain cobalt and arsenic; the ones with a more selected particles in the cross section, clarifying that the
1769

bluish-purple color show cobalt and phosphorous (Fig. 7). pigments used were magnesium cobalt arsenate, in both

J. Raman Spectrosc. 2012, 43, 1761–1771 Copyright © 2012 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/jrs
 F. Casadio et al.

Figure 7. Elemental maps, secondary electron and darkfield illumination images of a portion of the light purple layer in cross section 858 derived
from a sample excised from the light purple stripe of Pablo Picasso, The Red Armchair, 1931, (AIC 1957.72). (Illustrated in Fig. S5).

Conclusions
The acquisition of a comprehensive Raman spectral library of a
wide variety of reference cobalt-based green and violet artists’
pigments allowed the identification of the unknown green pig-
ment used by Jasper Johns as cobalt titanate green (C.I. PG 50).
This study represents the first documented evidence of the pres-
ence of cobalt titanate green in a contemporary artist’s palette,
and the compound’s complete vibrational features are fully illus-
trated here. Although the five reference commercial samples of
PG 50 showed similar FTIR and XRD patterns, some differences
among the manufacturers were highlighted, because of the pres-
ence of additives (i.e. BaSO4 in the Kremer pigment) or other
metal ions such as Sb, Zn, and Fe included in the spinel struc-
ture of the compound as a result of the manufacturing process.
In the Picasso painting, a mixture of cobalt violet light (mag-
nesium cobalt arsenate, Mg3-xCox(AsO4)2 and hydrated forms)
Figure 8. Raman spectra of (a) Lefranc cobalt violet (V8) (50 s, five times, and dark (cobalt phosphate, Co3(PO4)2) were identified.
l0 = 633 nm); and (b) Pablo Picasso, The Red Armchair, 1931, (AIC 1957.72) These case studies illustrate not only the analytical chal-
purple pigment particle on cross section 858 (120 s, one time, lenges related to the identification of modern pigments but
l0 = 785 nm, after multipoint baseline correction, and smoothing); (c) Pablo also the importance of having reliable and extensive collec-
Picasso, The Red Armchair, 1931, (AIC 1957.72) purple pigment particle on
tions of reference spectra. To date, despite seminal work on
cross section 858 (240 s, one time, l0 = 785 nm, after multipoint baseline
correction, and smoothing; peaks marked with an asterisk are assigned to Raman and FT-Raman spectroscopy of pigments, binding
zinc white – 438 cm 1 – and gypsum – 1008 cm 1 – also present in the media and other materials of relevance to those studying the
paint layer); (d) Kremer cobalt violet dark (120 s, two times, l0 = 633 nm). material make-up of cultural heritage objects and sites, the
spectra of cobalt-based green and violet pigments were lack-
un-hydrated and hydrated forms, as well as cobalt phos- ing and no easy-to-go reference was available that could allow
phate, as illustrated in Fig. 8 after matching with suitable unambiguous identification of these pigments in unknown
1770

references. samples. Thus, this research advances our knowledge of the

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Picasso to Johns: a Raman study of cobalt-based synthetic inorganic pigments

Raman characterization of synthetic cobalt-based artists’ pig- [3] N. C. Scherrer, S. Zumbuehl, F. Delavy, A. Fritsch, R. Kuehnen, Spectro-
ments, adding valuable data to the recently published database chim. Acta, Part A. 2009, 73, 505.
[4] P. Vandenabeele, L. Moens, H. G. M. Edwards, R. Dams, J. Raman
of cobalt-blue pigments,[14] and provides important elements for Spectrosc. 2000, 31, 509.
the documentation of notable occurrences of these pigments in [5] S. A. Centeno, V. Lladó Buisan, P. Ropret, J. Raman Spectrosc. 2006,
actual artworks. 37, 1111.
This study of cobalt violet pigments also allows the clarification [6] F. Casadio, M. Leona, J. R. Lombardi, R. P. Van Duyne, Accounts Chem.
Research. 2010, 43, 782.
of hydration states and composition for pigments of the Forbes [7] M. De Keijzer, In Preprints of 9th Triennial Meeting of The ICOM
collection that are widely shared by the cultural heritage science Committee for Conservation, (Ed.: K Grimstad), ICOM Committee for
community in the USA. Future experiments on the preparation Conservation, Los Angeles, 1990, pp. 214–219.
and heating of hydrated cobalt phosphates and magnesium [8] E. M. Suzuki, M. Carrabba, J. Forensic Sci. 2001, 46, 1053.
[9] G. Gautier, I. Fiedler, F. Casadio, K. Keegan, K. Lister, In Book of
cobalt arsenates may help to address whether the presence of
Abstracts of the Eighth Biennial Conference of the Infrared and
mixtures of anhydrous and hydrated versions may be a result Raman Users Group, Vienna, 2008, p. 101.
of variability in the manufacturing process or intentional mixing [10] A. Bezúr, K. Muir In Book of Abstracts of the Eighth Biennial Confer-
of two distinct pigments. ence of the Infrared and Raman Users Group, Vienna, 2008, p. 96.
[11] K. Keegan, K. Lister, In Jasper Johns: Gray, The Art Institute Of Chicago,
Yale University Press, New Haven and London, 2007, pp. 162–173.
[12] G. Gautier, A. Bezur, K. Muir, F. Casadio, I. Fiedler, Applied Spectrosc.
Acknowledgements 2009; 63, 597.
[13] K. Muir, A. Langley, A. Bezur, F. Casadio, J. Delaney, G. Gautier, J. Am.
The authors would like to thank the A. W. Mellon Foundation, Jerrold Institute Cons. forthcoming.
A. Carsello, Douglas Druick, Stephanie D’Alessandro, James [14] M. Bouchard, A. Gambardella, J. Raman Spectrosc. 2010, 41, 1477.
Rondeau, Allison Langley, Kelly Keegan, Kristin Lister, James Meyer, [15] R. L. Frost, W. Martens, J. T. Kloprogge, Spectrochim. Acta, Part A.
Jamie Stukenberg, Joseph Barabe, the Shepherd Color Corporation, 2004, 60, 343.
[16] W. Martens, R. L. Frost, J. T. Kloprogge, J. Raman Spectrosc. 2003,
and the Ferro Corporation. Scanning electron microscopy with 34, 90.
energy dispersive x-ray analysis was performed in the EPIC facility [17] M.-C. Corbeil, J.-P. Charland, E. A. Moffatt, Stud. Cons. 2002, 47, 237.
of NUANCE Center at Northwestern University. NUANCE Center is [18] G. Burrafato, M. Calabrese, A. Cosentino, A. Gueli, S. Troja, A. Zuccarello,
supported by NSF-NSEC, NSF-MRSEC, Keck Foundation, the State J. Raman Spectrosc. 2004, 35, 879.
of Illinois, and Northwestern University. The Serafy Foundation is [19] J. R. Hackman, In Pigment Handbook, Vol. 1. Properties and Economics
(Ed. P. A. Lewis), 2nd edition, Wiley-Interscience Publication, New York,
thanked for support of research and instrumentation at the Univer- 1988, pp. 403–408.
sity of Texas at Brownsville. Gwénaëlle Gautier and Rossella Croce [20] W. J. Cauwenberg, 1934, US Patent, 1,969,061.
are gratefully acknowledged for preliminary analytical work on [21] T. Böhland, K. Brandt, H. Brussaard, D. Calvert, G. Etzrodt, H. Rieck, O.
the Jasper Johns and cobalt violet pigments. Anna Vila, Nathalie Seeger, H. Wienand, J. Wiese, G. Buxbaum, Industrial Inorganic Pig-
ments, (Eds.: G. Buxbaum, G. Pfaff), 3rd edition, Wiley-VCH Verlag
Balcar, Gilles Barabant and staff at the C2RMF in Paris are thanked
GmbH & Co., KGaA, Weinheim, FRG, 2005, pp. 116–120.
for making available a sample of an historical Lefranc paint tube [22] Colour Index, The Society of Dyers and Colourists and the Ameri-
of Violet de Cobalt. can Association of Textile Chemists and Colorists, 1982; 7, pp.
7178–7179, 7289.
[23] N. Eastaugh, V. Walsh, T. Chaplin, R. Siddall, Pigment Compendium: A
ENDNOTES Dictionary of Historical Pigments, Elsevier Butterworth-Heinemann,
Oxford, 2004, pp. 114–116.
1. James Meyer to Kelly Keegan (Art Institute of Chicago), Private [24] G. W. Zhou, Y. S. Kang, Mat. Science Eng. C 2004, 24, 71.
communication, via email, March 17, 2008. [25] F. Pacheco, M. Gonzalez, A. Medina, S. Velumani, J. A. Ascencio, Appl.
Phys. A: Mater. Sci. Process. 2004, 78, 531.
2. The Forbes’ Pigment Collection is a reference study collection [26] CAMEO (Conservation and Art Materials Encyclopedia Online).
of over 1000 colorants assembled in the 1930s by Edward Museum of Fine Arts, Boston. www.mfa.org/cameo (accessed 12/
Waldo Forbes, formerly Director of the Fogg Art Museum at 12/2011).
Harvard University (1909–1945). Although the core collection [27] L. Burgio, R. J. H. Clark, Spectrochim. Acta, Part A. 2001, 57, 1491.
[28] An Infrared Spectroscopy Atlas for the Coatings Industry, 4th Edition,
of pigments is housed in the Straus Center for Conservation Vol. II, Federation of Societies for Coatings Technology, Pennsylvania,
at Harvard University, subsets of the materials are preserved USA, 1991, p. 562.
in nineteen institutions worldwide and are widely used and [29] E. M. Suzuki, M. X. McDermot, J. Forensic Sci. 2006, 51, 532.
shared as reference samples. [30] E. M. Suzuki, J. Forensic Sci. 1996, 41, 393.
[31] G. W. Zhou, D. K. Lee, Y. H. Kim, C. W. Kim, Y. S. Kang, Bull. Korean
Chem. Soc. 2006, 27, 368.
Supporting information [32] G. W. Zhou, Y. S. Kang, Mater. Sci. Eng. C 2004, 24, 71.
[33] M. I. Baraton, G. Busca, M. C. Prieto, G. Ricchiardi, V. Sanchez Escribano,
Supporting information may be found in the online version of J. Solid State Chem. 1994, 112, 9.
this article. [34] E. Mwenesongole, A Raman- and XRD study of the crystal chemis-
try of cobalt blue, University of Pretoria, 2008. (Dissertation avail-
able at http://upetd.up.ac.za/thesis/available/etd-11292009-214916/
References unrestricted/dissertation.pdf accessed 2/14/2012).
[35] N. Bahlawane, P. Herve T. Ngamou, V. Vannier, T. Kottke, J. Heberle,
[1] P. Vandenabeele, H. G. M. Edwards, L. Moens, Chem. Reviews. 2007, K. Kohse-Höinghaus, Phys. Chem. Chem. Phys. 2009, 11, 9224.
107, 675. [36] B. Piriou, J. F. Poullen, J. Raman Spectrosc. 1984, 15, 343.
[2] G. D. Smith, R. J. H. Clark, J. Archaeol. Science. 2004, 31, 1137. [37] W. P. Griffith, J. Chem. Soc. A 1970, 286.
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